CN114044847A - High-water-resistance and stain-resistant acrylate emulsion and preparation method thereof - Google Patents
High-water-resistance and stain-resistant acrylate emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN114044847A CN114044847A CN202111381975.XA CN202111381975A CN114044847A CN 114044847 A CN114044847 A CN 114044847A CN 202111381975 A CN202111381975 A CN 202111381975A CN 114044847 A CN114044847 A CN 114044847A
- Authority
- CN
- China
- Prior art keywords
- parts
- emulsion
- resistance
- water
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a high-water-resistance and stain-resistant acrylate emulsion and a preparation method thereof, belonging to the technical field of synthesis of water-based resin; the preparation method comprises the following preparation steps: uniformly mixing a part of deionized water with a part of anionic emulsifier, nonionic emulsifier, initiator, butyl acrylate, acrylic acid, styrene, hydroxyethyl acrylate, vinyl acetate, epoxy monomer and silane coupling agent, and stirring at a high speed to prepare milky pre-emulsion; then adding the rest deionized water, the rest anionic emulsifier, the buffer and a part of pre-emulsion into a reaction kettle, heating and carrying out polymerization reaction to obtain seed emulsion; and finally, uniformly dropwise adding the residual pre-emulsion into the seed emulsion, neutralizing by using a neutralizing agent, filtering and discharging to obtain the high-water-resistance and dirt-resistance acrylate emulsion. Compared with the existing water-based coating material, the acrylate emulsion prepared by the invention improves the water resistance of the coating, reduces the dosage of the emulsifier and the curing agent, reduces the surface energy and improves the dirt resistance.
Description
Technical Field
The invention relates to a self-crosslinking organic silicon modified acrylic emulsion and a preparation method thereof, in particular to a high-water-resistance and stain-resistant acrylic emulsion and a preparation method thereof, belonging to the technical field of synthesis of water-based resin.
Background
With the application and research progress of the acrylate copolymer emulsion and the increasing requirement on environmental protection, the acrylate copolymer emulsion is widely used as a coating film forming agent and a textile printing and dyeing adhesive. The acrylic ester solvent-based paint on the sports ground uses a large amount of organic solvents and raw materials, releases a large amount of harmful substances such as benzene and aldehydes in the using process, and is harmful to the health of people.
The water-based acrylate is a green environment-friendly emulsion and is widely applied to the fields of home coating removal, building decoration and the like. However, the existing water-based acrylate coating uses a large amount of emulsifier in order to keep the stability of the system, so that the water resistance of the water-based coating is deteriorated while the system is stabilized; meanwhile, in order to improve the adhesive force between the coating and a base material, a large amount of functional monomers containing hydroxyl and carboxyl are introduced into the formula, and the existence of the polar monomers can cause the water resistance to be reduced and the surface polarity of the coating to be higher, so that the surface of the coating is easy to absorb impurities such as dust and the like, and the abrasion resistance can be rapidly reduced after a period of time, and the attractiveness is influenced. In general horizontal coating application, in order to improve the wear resistance of the coating, a large amount of curing agent is often required to be added, so that the wear resistance of the coating is ensured, and the cost is greatly improved.
Disclosure of Invention
The purpose of the invention is: the defects of the existing acrylic ester coating on the sports ground on the water resistance and the dirt resistance are overcome, the acrylic ester emulsion with high water resistance and dirt resistance and the preparation method are provided, and the anionic emulsifier and the nonionic emulsifier are matched in the formula, so that the stability of the system is ensured, and the dosage of the emulsifier is reduced and the water resistance is improved; the adhesive force and the water resistance of the epoxy monomer are improved; by introducing the silane coupling agent to perform polymerization reaction with the acrylate monomer and performing coupling reaction with the inorganic substance, a bonding layer of an organic matrix, the silane coupling agent and the inorganic matrix can be formed, and the surface energy of the coating is reduced, so that impurities such as dust and the like are not easily adsorbed on the surface of the coating, the dirt resistance of the coating is improved, the using amount of the curing agent is greatly reduced, and the using cost is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of an acrylate emulsion with high water resistance and stain resistance comprises the following preparation steps:
s1, pre-emulsification: dissolving 5-20 parts of epoxy group monomer by using 50-100 parts of butyl acrylate, then uniformly mixing 30-60% of deionized water with 2-6 parts of anionic emulsifier, 2-5 parts of nonionic emulsifier, 0.8-1.6 parts of initiator, 2-4 parts of acrylic acid, 10-80 parts of vinyl acetate, 20-80 parts of styrene, 10-20 parts of hydroxyethyl acrylate, 1-5 parts of silane coupling agent and butyl acrylate and epoxy group monomer dissolved solution in parts by weight, stirring the mixed solution at a high speed of 1000r/min, pre-emulsifying for 30min to obtain stable milky pre-emulsion;
s2, seed polymerization: adding the rest 40-70% of deionized water, the rest 50% of anionic emulsifier, 0.4-0.8 part of buffering agent and 10-25% of the total amount of the pre-emulsion into a reaction kettle, starting heating under the stirring condition of 200-500 r/min, preserving heat for 30min when the temperature reaches 75-85 ℃, and obtaining seed emulsion after the base material in the reaction kettle turns blue;
s3, polymerization: uniformly dropwise adding the remaining 75-90% of pre-emulsion into the seed emulsion within 3h, preserving heat for 2h after dropwise adding is finished, then cooling to 50 ℃, dropwise adding 3-16 parts of neutralizing agent into the seed emulsion within 10min, preserving heat for 30min, controlling the pH to be 6.5-8.5, filtering and discharging after cooling, and obtaining the high-water-resistance and dirt-resistance acrylate emulsion.
The high-water-resistance and dirt-resistance acrylate emulsion is prepared from the following raw materials in parts by weight:
50-100 parts of butyl acrylate,
2-4 parts of acrylic acid,
20-80 parts of styrene,
10-80 parts of vinyl acetate,
10-20 parts of hydroxyethyl acrylate
5-20 parts of epoxy monomer,
1-5 parts of silane coupling agent,
2-6 parts of anionic emulsifier,
2-5 parts of non-ionic emulsifier,
0.8 to 1.6 portions of initiator,
0.4 to 0.8 part of a buffer,
150-400 parts of deionized water,
3-16 parts of a neutralizing agent.
The acrylic acid is methacrylic acid or acrylic acid.
The hydroxyethyl acrylate is hydroxyethyl acrylate or hydroxyethyl methacrylate.
The epoxy group monomer is a monomer or epoxy resin with vinyl and an epoxy group, the epoxy monomer with the vinyl comprises glycidyl acrylate and glycidyl methacrylate, and the epoxy resin comprises epoxy resin E-44 and epoxy resin E-51.
The silane coupling agent is vinyl triethoxysilane A151, vinyl trimethoxysilane A171 or vinyl tri (beta-methoxyethoxy) silane A172.
The initiator is ammonium persulfate or potassium persulfate.
The buffer is sodium bicarbonate, sodium dihydrogen phosphate or sodium acetate.
The neutralizing agent is one or a mixed solution of ammonia water and triethylamine.
A high-water-resistance and stain-resistant acrylate emulsion is prepared by the preparation method.
The invention has the beneficial effects that:
1) in the preparation process, the monomer or the epoxy resin with vinyl and epoxy groups is used, the vinyl and the acrylate monomer are subjected to polymerization reaction, and the epoxy group (-CH (O) CH-) is subjected to crosslinking reaction due to the ring opening of the three-membered ring in high tension, so that the water resistance of the epoxy resin is greatly improved; the introduction of epoxy monomer also improves the material selectivity and reduces the cost of the emulsion.
2) In the preparation process, styrene is used as a hard monomer, carbon-carbon double bonds (-C ═ C-) on the styrene can be subjected to polymerization reaction with other acrylic monomers, and phenyl (C6H5-) exposed at the outer side has hydrophobicity, so that the water resistance and the wear resistance of the emulsion can be greatly improved in a formula.
3) In the preparation process, silane coupling agent Y-R-Si (OR)3 (Y-organic functional group, SiOR-siloxy) can be polymerized with acrylate monomer so as to have reactivity or compatibility with organic matters, silanol (Si (OH)3) is generated when the (SiOR-siloxy) is hydrolyzed, the silanol can be coupled with inorganic substances to form siloxane so as to improve the adhesion with a base material, and the water resistance of the coating can be improved by the hydrophobic effect of (R-methoxy/ethoxy), so that when the silane coupling agent is between an inorganic interface and an organic interface, an organic matrix-silane coupling agent-inorganic matrix binding layer can be formed, the surface energy of a coating is reduced, and the water resistance and the dirt resistance of acrylate emulsion are greatly improved, so that impurities such as dust and the like are not easy to adsorb on the surface of the coating, and the service life of the coating is prolonged.
4) The preparation method combines the pre-emulsification and seed polymerization processes, adopts the anionic emulsifier and the nonionic emulsifier in combination, and reduces the use amount of the emulsifier to be below 4% compared with the single use of the anionic emulsifier or the nonionic emulsifier, so that the obtained emulsion has more uniform particle size distribution, more stable system, lower gel rate and longer storage period.
5) In the preparation method, the initiator, the monomer, the water and part of the emulsifier are emulsified together, the traditional mode of respectively dripping the monomer and the initiator is abandoned, the production process is simplified, the monomer and the initiator are polymerized in the emulsion in the same proportion, the molecular weight distribution is narrower and more uniform, and the formula stability is ensured.
6) According to the invention, as the acrylic acid monomer is used in the formula, the emulsion is acidic, the emulsifying property of the emulsifier is destroyed, and the stability and the storage period of the system are reduced, so that the viscosity of the system can be adjusted and the rheological property can be improved by using the mixed neutralizer of ammonia water and triethylamine in the preparation process while the stability of the system is improved; the use of the neutralizing agent can adjust the viscosity of the system and prolong the storage period, and compared with the method of not using the neutralizing agent for neutralization, the storage period can be prolonged from 30 days to more than 180 days by using the neutralizing agent to adjust the PH to 8.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below.
Through specific experiments and researches of the inventor, the following results are obtained: acrylic acid or methacrylic acid, hydroxyethyl acrylate or hydroxyethyl methacrylate, epoxy resin, glycidyl methacrylate or glycidyl acrylate and a silane coupling agent in a formula system can be used as a crosslinking agent in a reaction system, and a polymerization crosslinking grafting reaction is carried out under the joint use of an initiator and the reaction temperature, so that groups such as hydroxyl, carboxyl, epoxy, siloxy and the like are introduced into the formula system, the adhesive force between the formula system and a base material can be obviously improved, and the water resistance of the coating can be improved and the surface energy of the coating can be reduced due to the hydrophobic effect of (R-methoxy/ethoxy) in the silane coupling agent, so that the wear resistance, the water resistance and the dirt resistance of the coating in use are improved.
The anionic emulsifier in the formula system is alkyl sulfate, and the nonionic emulsifier refers to alkylphenol polyoxyethylene.
Example 1: the formula of the raw materials for preparing the high-water-resistance and dirt-resistance acrylate emulsion is shown in the table 1:
the preparation method for preparing the acrylate emulsion according to the formula shown in the table 1 comprises the following preparation steps:
s1, pre-emulsification: dissolving 5 parts of epoxy resin E-44 by using 60 parts of butyl acrylate, then uniformly mixing 50 parts of deionized water with 1 part of anionic emulsifier, 2 parts of nonionic emulsifier, 1 part of ammonium persulfate, 3 parts of acrylic acid, 50 parts of styrene, 40 parts of vinyl acetate, 10 parts of hydroxyethyl acrylate, 1.8 parts of silane coupling agent and a solution of butyl acrylate and epoxy resin E-44 by weight parts, stirring the mixed solution at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable milky pre-emulsion;
s2, seed polymerization: adding the rest 100 parts of deionized water, the rest 3 parts of anionic emulsifier, 0.4 part of sodium bicarbonate and 20 parts of pre-emulsion into a reaction kettle, starting heating under the stirring condition of 200r/min, preserving heat for 30min when the temperature reaches 82 ℃, and obtaining seed emulsion after the base material in the reaction kettle turns blue;
s3, polymerization: and uniformly dropwise adding the rest of pre-emulsion into the seed emulsion within 3h, preserving heat for 2h after dropwise adding is finished, cooling to 50 ℃, dropwise adding 3 parts of triethylamine and 12 parts of ammonia water into the emulsion within 10min, preserving heat for 30min, measuring the pH to be 8, cooling, filtering and discharging to obtain the product, namely the high-water-resistance and dirt-resistance acrylate emulsion.
The acrylate emulsion prepared in example 1 was subjected to property testing to obtain the following property testing table 1:
| detecting items | Performance of |
| Solid content | 53.0％ |
| Viscosity of the oil | 1220cp |
| Appearance of the product | Yellowish translucent |
| Water resistance (25 ℃, 24h) | Without light loss |
| Stain resistance (reflectance change/%) | 10％ |
| Hardness of pencil | >3H |
| PH | 8 |
Example 2: the formula of the raw materials for preparing the high-water-resistance and dirt-resistance acrylate emulsion is shown in the table 2:
the preparation method for preparing the acrylate emulsion according to the formula shown in the table 2 comprises the following preparation steps:
s1, pre-emulsification: dissolving 5 parts of epoxy resin E-44 by using 60 parts of butyl acrylate, then uniformly mixing 50 parts of deionized water with 1 part of anionic emulsifier, 2 parts of nonionic emulsifier, 1 part of ammonium persulfate, 3 parts of acrylic acid, 50 parts of styrene, 40 parts of vinyl acetate, 10 parts of hydroxyethyl acrylate, 1.0 part of silane coupling agent and a solution of butyl acrylate and epoxy resin E-44 by weight parts, stirring the mixed solution at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable milky pre-emulsion;
s2, seed polymerization: adding the rest 100 parts of deionized water, the rest 3 parts of anionic emulsifier, 0.4 part of sodium bicarbonate and 20 parts of pre-emulsion into a reaction kettle, starting heating under the stirring condition of 200r/min, preserving heat for 30min when the temperature reaches 82 ℃, and obtaining seed emulsion after the base material in the reaction kettle turns blue;
s3, polymerization: and uniformly dropwise adding the rest of pre-emulsion into the seed emulsion within 3h, preserving heat for 2h after dropwise adding is finished, cooling to 50 ℃, dropwise adding 3 parts of triethylamine and 12 parts of ammonia water into the emulsion within 10min, preserving heat for 30min, measuring the pH to be 8, cooling, filtering and discharging to obtain the product, namely the high-water-resistance and dirt-resistance acrylate emulsion.
The acrylate emulsion prepared in example 2 was subjected to property testing to obtain the following property testing table 2:
| detecting items | Performance of |
| Solid content | 52.8％ |
| Viscosity of the oil | 1200cp |
| Appearance of the product | Yellowish translucent |
| Water resistance (25 ℃, 24h) | Very slight loss of light |
| Stain resistance (reflectance change/%) | 15％ |
| Hardness of pencil | >3H |
| PH | 8 |
Example 3: the formula of the raw materials for preparing the high-water-resistance and dirt-resistance acrylate emulsion is shown in table 3 as follows:
the preparation method for preparing the acrylate emulsion according to the formula shown in the table 3 comprises the following preparation steps:
s1, pre-emulsification: dissolving 10 parts of epoxy resin E-44 by using 100 parts of butyl acrylate, then uniformly mixing 100 parts of deionized water, 2.5 parts of anionic emulsifier, 2 parts of nonionic emulsifier, 1.2 parts of ammonium persulfate, 3.7 parts of acrylic acid, 80 parts of styrene, 10 parts of vinyl acetate, 10 parts of hydroxyethyl acrylate, 2 parts of silane coupling agent and a solution of butyl acrylate and epoxy resin E-44 by weight parts, stirring the mixed solution at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable milky pre-emulsion;
s2, seed polymerization: adding the rest 120 parts of deionized water, the rest 3.5 parts of anionic emulsifier, 0.6 part of sodium bicarbonate and 60 parts of pre-emulsion into a reaction kettle, starting heating under the stirring condition of 200r/min, preserving heat for 30min when the temperature reaches 80 ℃, and obtaining seed emulsion after the base material in the reaction kettle turns blue;
s3, polymerization: and uniformly dropwise adding the rest of pre-emulsion into the seed emulsion within 3h, preserving heat for 2h after dropwise adding is finished, cooling to 50 ℃, dropwise adding 4 parts of triethylamine and 12 parts of ammonia water into the seed emulsion within 10min, preserving heat for 30min, measuring the pH to be 8, cooling, filtering and discharging to obtain the product, namely the high-water-resistance and stain-resistance acrylate emulsion.
The acrylate emulsion prepared in example 3 was subjected to property testing to obtain the following property testing table 3:
example 4: the formula of the raw materials for preparing the high-water-resistance and dirt-resistance acrylate emulsion is shown in table 4 as follows:
| name of raw materials | Quality (g) |
| Butyl acrylate BA | 100.0 |
| Acrylic acid AA | 3.7 |
| Styrene MMA | 80.0 |
| Vinyl acetate VAc | 10.0 |
| Hydroxyethyl acrylate HEA | 15.0 |
| Epoxy resin E-44 | 10.0 |
| Silane coupling agent YDH-171 | 2.0 |
| Alkyl sulfates | 6.0 |
| Alkylphenol ethoxylates | 2.0 |
| Ammonium persulfate APS | 1.2 |
| Sodium bicarbonate NaHCO3 | 0.6 |
| Deionized water | 220.0 |
| Ammonia (10%) | 12.0 |
| Triethylamine TEA | 4.0 |
The preparation method for preparing the acrylate emulsion according to the formula shown in table 4 comprises the following preparation steps:
s1, pre-emulsification: dissolving 10 parts of epoxy resin E-44 by using 100 parts of butyl acrylate, then uniformly mixing 100 parts of deionized water, 2.5 parts of anionic emulsifier, 2 parts of nonionic emulsifier, 1.2 parts of ammonium persulfate, 3.7 parts of acrylic acid, 80 parts of styrene, 10 parts of vinyl acetate, 10 parts of hydroxyethyl acrylate, 2 parts of silane coupling agent and a solution of butyl acrylate and epoxy resin E-44 by weight parts, stirring the mixed solution at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable milky pre-emulsion;
s2, seed polymerization: adding the rest 120 parts of deionized water, the rest 3.5 parts of anionic emulsifier, 0.6 part of sodium bicarbonate and 60 parts of pre-emulsion into a reaction kettle, starting heating under the stirring condition of 200r/min, preserving heat for 30min when the temperature reaches 80 ℃, and obtaining seed emulsion after the base material in the reaction kettle turns blue;
s3, polymerization: and uniformly dropwise adding the rest part of pre-emulsion into the seed emulsion within 3h, preserving heat for 2h after dropwise adding is finished, cooling to 50 ℃, dropwise adding 4 parts of triethylamine and 12 parts of ammonia water into the seed emulsion within 10min, preserving heat for 30min, measuring the pH to be 8, cooling, filtering and discharging to obtain the product, namely the high-water-resistance and stain-resistant acrylate emulsion.
The acrylate emulsion prepared in example 4 was subjected to property testing to obtain the following property testing table 4:
| detecting items | Performance of |
| Solid content | 49.4％ |
| Viscosity of the oil | 1150cp |
| Appearance of the product | Opalescent translucency |
| Water resistance (25 ℃, 24h) | Without light loss |
| Stain resistance (reflectance change/%) | 12％ |
| Hardness of pencil | >3H |
| PH | 8 |
Example 5: the formula of the raw materials for preparing the high-water-resistance and dirt-resistance acrylate emulsion is shown in table 5:
| name of raw materials | Quality (g) |
| Butyl acrylate BA | 70.0 |
| Acrylic acid AA | 4.0 |
| Styrene MMA | 70.0 |
| Vinyl acetate VAc | 75.0 |
| Hydroxyethyl acrylate HEA | 15.0 |
| Epoxy resin E-44 | 15.0 |
| Silane coupling agent YDH-171 | 3.0 |
| Alkyl sulfates | 6.0 |
| Alkylphenol ethoxylates | 3.0 |
| Ammonium persulfate APS | 1.5 |
| Sodium bicarbonate NaHCO3 | 0.7 |
| Deionized water | 400.0 |
| Ammonia (10%) | 12.0 |
| Triethylamine TEA | 4.0 |
The preparation method for preparing the acrylate emulsion according to the formula shown in table 5 comprises the following preparation steps:
s1, pre-emulsification: dissolving 15 parts of epoxy resin E-44 by using 70 parts of butyl acrylate, then uniformly mixing 130 parts of deionized water with 3 parts of anionic emulsifier, 3 parts of nonionic emulsifier, 1.5 parts of ammonium persulfate, 4 parts of acrylic acid, 70 parts of styrene, 75 parts of vinyl acetate, 15 parts of hydroxyethyl acrylate, 3 parts of silane coupling agent and a solution of butyl acrylate and epoxy resin by weight parts, stirring the mixed solution at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable milky pre-emulsion;
s2, seed polymerization: adding the rest 270 parts of deionized water, the rest 3 parts of anionic emulsifier, 0.7 part of sodium bicarbonate and 70 parts of pre-emulsion into a reaction kettle, starting heating under the stirring condition of 200r/min, preserving heat for 30min when the temperature reaches 82 ℃, and obtaining seed emulsion after the base material in the reaction kettle turns blue;
s3, polymerization: and uniformly dropwise adding the rest of pre-emulsion into the seed emulsion within 3h, preserving heat for 2h after dropwise adding is finished, cooling to 50 ℃, dropwise adding 4 parts of triethylamine and 12 parts of ammonia water into the seed emulsion within 10min, preserving heat for 30min, measuring the pH to be 8, cooling, filtering and discharging to obtain the product, namely the high-water-resistance and stain-resistance acrylate emulsion.
The acrylate emulsion prepared in example 5 was subjected to a performance test to obtain the following performance test table 5:
| detecting items | Performance of |
| Solid content | 39.5％ |
| Viscosity of the oil | 110cp |
| Appearance of the product | Yellowish translucent |
| Water resistance (25 ℃, 24h) | Without light loss |
| Stain resistance (reflectance change/%) | 14％ |
| Hardness of pencil | >5H |
| PH | 8 |
Example 6: the formula of the raw materials for preparing the high-water-resistance and dirt-resistance acrylate emulsion is shown in table 6 as follows:
the preparation method for preparing the acrylate emulsion according to the formula shown in table 6 comprises the following preparation steps:
s1, pre-emulsification: dissolving 7.5 parts of epoxy resin E-44 by using 70 parts of butyl acrylate, then uniformly mixing 130 parts of deionized water with 3 parts of anionic emulsifier, 3 parts of nonionic emulsifier, 1.5 parts of ammonium persulfate, 4 parts of acrylic acid, 70 parts of styrene, 75 parts of vinyl acetate, 15 parts of hydroxyethyl acrylate, 3 parts of silane coupling agent and a solution of butyl acrylate and epoxy resin E-44 by weight parts, stirring the mixed solution at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable milky pre-emulsion;
s2, seed polymerization: adding the rest 270 parts of deionized water, the rest 3 parts of anionic emulsifier, 0.7 part of sodium bicarbonate and 70 parts of pre-emulsion into a reaction kettle, starting heating under the stirring condition of 200r/min, preserving heat for 30min when the temperature reaches 82 ℃, and obtaining seed emulsion after the base material in the reaction kettle turns blue;
s3, polymerization: and uniformly dropwise adding the residual 319.5 parts of pre-emulsion into the seed emulsion within 3h, preserving heat for 2h after dropwise adding is finished, cooling to 50 ℃, dropwise adding 4 parts of triethylamine and 12 parts of ammonia water into the seed emulsion within 10min, preserving heat for 30min, measuring the pH to be 8, cooling, filtering and discharging to obtain the high-water-resistance and stain-resistance acrylate emulsion.
The acrylate emulsion prepared in example 6 was subjected to property testing to obtain the following property testing table 6:
| detecting items | Performance of |
| Solid content | 39.7％ |
| Viscosity of the oil | 110cp |
| Appearance of the product | Yellowish translucent |
| Water resistance (25 ℃, 24h) | Without light loss |
| Stain resistance (reflectance change/%) | 14％ |
| Hardness of pencil | >4H |
| PH | 8 |
Example 7: the raw material formula for preparing the high water-resistant and dirt-resistant acrylate emulsion is shown in table 7 as follows:
the preparation method for preparing the acrylate emulsion according to the formula shown in table 7 comprises the following preparation steps:
s1, pre-emulsification: dissolving 15 parts of glycidyl methacrylate by using 60 parts of butyl acrylate, then uniformly mixing 130 parts of deionized water with 3 parts of anionic emulsifier, 3 parts of nonionic emulsifier, 1.5 parts of ammonium persulfate, 4 parts of acrylic acid, 80 parts of styrene, 75 parts of vinyl acetate, 15 parts of hydroxyethyl acrylate, 3 parts of silane coupling agent and a solution of butyl acrylate and glycidyl methacrylate by weight parts, stirring the mixed solution at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable milky pre-emulsion;
s2, seed polymerization: adding the rest 270 parts of deionized water, the rest 3 parts of anionic emulsifier, 0.7 part of sodium bicarbonate and 70 parts of pre-emulsion into a reaction kettle, starting heating under the stirring condition of 200r/min, preserving heat for 30min when the temperature reaches 82 ℃, and obtaining seed emulsion after the base material in the reaction kettle turns blue;
s3, polymerization: and uniformly dropwise adding the rest of pre-emulsion into the seed emulsion within 3h, preserving heat for 2h after dropwise adding is finished, cooling to 50 ℃, dropwise adding 4 parts of triethylamine and 12 parts of ammonia water into the seed emulsion within 10min, preserving heat for 30min, measuring the pH to be 8, cooling, filtering and discharging to obtain the product, namely the high-water-resistance and stain-resistance acrylate emulsion.
The acrylate emulsion prepared in example 7 was subjected to property testing to obtain the following property testing table 7:
| detecting items | Performance of |
| Solid content | 39.7％ |
| Viscosity of the oil | 80cp |
| Appearance of the product | Milky white with blue light |
| Water resistance (25 ℃, 24h) | Without change |
| Stain resistance (reflectance change/%) | 8％ |
| Hardness of pencil | >6H |
| PH | 8 |
Example 8: the formula of the raw materials for preparing the high-water-resistance and dirt-resistance acrylate emulsion is shown in table 8:
the preparation method for preparing the acrylate emulsion according to the formula shown in the table 8 comprises the following preparation steps:
s1, pre-emulsification: dissolving 20 parts of epoxy resin E-44 by using 50 parts of butyl acrylate, then uniformly mixing 50 parts of deionized water with 4 parts of nonionic emulsifier, 1 part of ammonium persulfate, 2 parts of acrylic acid, 20 parts of styrene, 80 parts of vinyl acetate, 20 parts of hydroxyethyl acrylate, 5 parts of silane coupling agent and a solution of butyl acrylate and epoxy resin E-44 in parts by weight, stirring the mixed solution at a high speed at the rotating speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable milky pre-emulsion;
s2, seed polymerization: adding the rest 100 parts of deionized water, 2 parts of anionic emulsifier, 0.4 part of sodium bicarbonate and 20 parts of pre-emulsion into a reaction kettle, starting heating under the stirring condition of 200r/min, preserving heat for 30min when the temperature reaches 82 ℃, and obtaining seed emulsion after the base material in the reaction kettle turns blue;
s3, polymerization: and uniformly dropwise adding the rest of the pre-emulsion into the seed emulsion within 3h, preserving heat for 2h after dropwise adding is finished, cooling to 50 ℃, dropwise adding 3 parts of triethylamine into the seed emulsion within 10min, preserving heat for 30min, measuring the pH to be 8, filtering and discharging after cooling, and thus obtaining the high-water-resistance and dirt-resistance acrylate emulsion.
The acrylate emulsion prepared in example 8 was subjected to a performance test to obtain the following performance test table 8:
with reference to the performance test results of the above examples: comparing example 1 with example 2, the amount of silane coupling agent is 1% of the total amount of monomers, the best water resistance is no light loss in the test of paint film light loss; when the amount of the silane coupling agent accounts for more than 1% of the total amount of the monomers, a small amount of gel exists in the system, and the water resistance is not obviously improved; when the content is less than 1%, the water resistance becomes good as the ratio of the silane coupling agent increases. In the stain resistance test of comparative example 1 and example 2, the proportion of the silane coupling agent in example 1 is high, and it can be seen that (reflectance change value/%) is small, indicating that the stain resistance of the acrylic emulsion is improved as the proportion of the silane coupling agent is increased.
Comparing example 3 with example 4, the pencil hardness of the paint film is tested to be hardened along with the increase of the proportion of hydroxyethyl acrylate, because the higher proportion of hydroxyethyl acrylate added with the same amount of curing agent in the using process means that the crosslinking density is higher, the higher the crosslinking density is, the better the hardness and the wear resistance of the paint film are, and the experiment proves that the hydroxyl value is preferably 45-60 mgKOH/g.
The pencil hardness of the paint film tested by comparing example 5 with example 6 with example 8 is high along with the height of the proportion of the epoxy resin, which shows that the wear resistance of the acrylic emulsion is increased along with the increase of the proportion of the epoxy resin, the weather resistance of example 8 is poorer than that of other formulas in an aging experiment test, and the weather resistance of the acrylic emulsion is easily reduced when the proportion of the epoxy resin is higher than that of 2-5% of the total amount of the acrylic monomer through the experiment test.
Comparing example 7 with the other examples, the emulsion in example 7 has the highest theoretical glass transition temperature and the highest pencil hardness tested. Therefore, the antifouling property of the resin is improved correspondingly with the higher the hardness of the resin, under the condition that the proportion of the silane coupling agent is unchanged. Comparing example 8 with other examples, the proportion of silane coupling agent in example 8 was the highest, but the soil resistance was not significantly improved.
Therefore, in conclusion, the adhesive force to various base materials is improved and the cohesive force of the resin is increased by introducing the epoxy functional monomer into the formula system. By introducing the silane coupling agent, (SiOR-siloxy) on the silane coupling agent forms siloxane to improve the adhesion with a base material, and the water resistance and the dirt resistance of the coating can be improved by the hydrophobic effect of (R-methoxy/ethoxy).
The invention combines the production process of pre-emulsification and seed polymerization, so that the process is simplified, the molecular weight distribution of the prepared acrylic emulsion is more uniform, the consistency of the product performance is ensured, and finally, the composite neutralizer is used to ensure easier storage and longer storage period.
The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A preparation method of acrylate emulsion with high water resistance and stain resistance is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
s1, pre-emulsification: dissolving 5-20 parts of epoxy group monomer by using 50-100 parts of butyl acrylate, then mixing 30-60% of deionized water with 2-6 parts of anionic emulsifier, 2-5 parts of nonionic emulsifier, 0.8-1.6 parts of initiator, 2-4 parts of acrylic acid, 20-80 parts of styrene, 10-80 parts of vinyl acetate, 10-20 parts of hydroxyethyl acrylate, 1-5 parts of silane coupling agent and butyl acrylate with the solution of epoxy group monomer by weight parts, stirring the mixed solution at a high speed of 1000r/min, pre-emulsifying for 30min to obtain stable milky pre-emulsion;
s2, seed polymerization: adding the rest 40-70% of deionized water, the rest 50% of anionic emulsifier, 0.4-0.8 part of buffering agent and 10-25% of the total amount of the pre-emulsion into a reaction kettle, starting heating under the stirring condition of 200-500 r/min, preserving heat for 30min when the temperature reaches 75-85 ℃, and obtaining seed emulsion after the base material in the reaction kettle turns blue;
s3, polymerization: uniformly dripping the remaining 75-90% of pre-emulsion into the seed emulsion within 3h, preserving heat for 2h after finishing dripping, cooling to 50 ℃, dripping 3-16 parts of neutralizing agent into the seed emulsion within 10min, preserving heat for 30min, controlling the pH to be 6.5-8.5, filtering and discharging after cooling to obtain a product, namely the high-water-resistance and dirt-resistance acrylate emulsion;
the high-water-resistance and dirt-resistance acrylate emulsion is prepared from the following raw materials in parts by weight:
50-100 parts of butyl acrylate,
2-4 parts of acrylic acid,
20-80 parts of styrene,
10-80 parts of vinyl acetate,
10-20 parts of hydroxyethyl acrylate,
5-20 parts of epoxy monomer,
1-5 parts of silane coupling agent,
2-6 parts of anionic emulsifier,
2-5 parts of non-ionic emulsifier,
0.8 to 1.6 portions of initiator,
0.4 to 0.8 part of a buffer,
150-400 parts of deionized water,
3-16 parts of a neutralizing agent.
2. The method for producing an acrylic ester emulsion according to claim 1, wherein: the acrylic acid is methacrylic acid or acrylic acid.
3. The method for producing an acrylic ester emulsion according to claim 1, wherein: the epoxy group monomer is a monomer or epoxy resin with vinyl and epoxy groups, the monomer with vinyl and epoxy groups comprises glycidyl acrylate and glycidyl methacrylate, and the epoxy resin comprises epoxy resin E-44 and epoxy resin E-51.
4. The method for producing an acrylic ester emulsion according to claim 1, wherein: the silane coupling agent is vinyl triethoxysilane A151, vinyl trimethoxysilane A171 or vinyl tri (beta-methoxyethoxy) silane A172.
5. The method for producing an acrylic ester emulsion according to claim 1, wherein: the initiator is ammonium persulfate or potassium persulfate.
6. The method for producing an acrylic ester emulsion according to claim 1, wherein: the buffer is sodium bicarbonate, sodium dihydrogen phosphate or sodium acetate.
7. The method for producing an acrylic ester emulsion according to claim 1, wherein: the neutralizing agent is one or a mixed solution of ammonia water and triethylamine.
8. A high-water-resistance and dirt-resistance acrylate emulsion is characterized in that: the acrylic ester emulsion according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111381975.XA CN114044847B (en) | 2021-11-18 | 2021-11-18 | High-water-resistance and dirt-resistance acrylate emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111381975.XA CN114044847B (en) | 2021-11-18 | 2021-11-18 | High-water-resistance and dirt-resistance acrylate emulsion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114044847A true CN114044847A (en) | 2022-02-15 |
| CN114044847B CN114044847B (en) | 2023-05-26 |
Family
ID=80210395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111381975.XA Active CN114044847B (en) | 2021-11-18 | 2021-11-18 | High-water-resistance and dirt-resistance acrylate emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114044847B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678374A (en) * | 2023-01-06 | 2023-02-03 | 山东世纪联合新材料科技有限公司 | Water-based heat insulation coating and preparation method thereof |
| CN116876221A (en) * | 2023-07-04 | 2023-10-13 | 广东创新精细化工实业有限公司 | Fluorine-free waterproof agent, preparation method thereof and application thereof in fabric |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814663A (en) * | 2005-02-05 | 2006-08-09 | 广州慧谷化学有限公司 | Thermo-setting acrylic-acid emulsion, its preparing method and paint containing same |
| CN101429267A (en) * | 2008-12-25 | 2009-05-13 | 海洋化工研究院 | Preparation and uses of epoxy/acrylic acid hybridisation emulsion |
| CN101525399A (en) * | 2009-03-27 | 2009-09-09 | 上海应用技术学院 | Polyacrylate emulsion with high water resistance and preparation method thereof |
| CN108484811A (en) * | 2018-02-28 | 2018-09-04 | 佛山市顺德区巴德富实业有限公司 | A kind of solvent resistant acrylic emulsion and preparation method thereof |
| CN112300318A (en) * | 2020-11-10 | 2021-02-02 | 三棵树(上海)新材料研究有限公司 | Environment-friendly room-temperature self-crosslinking acrylate emulsion, preparation method and application thereof |
-
2021
- 2021-11-18 CN CN202111381975.XA patent/CN114044847B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814663A (en) * | 2005-02-05 | 2006-08-09 | 广州慧谷化学有限公司 | Thermo-setting acrylic-acid emulsion, its preparing method and paint containing same |
| CN101429267A (en) * | 2008-12-25 | 2009-05-13 | 海洋化工研究院 | Preparation and uses of epoxy/acrylic acid hybridisation emulsion |
| CN101525399A (en) * | 2009-03-27 | 2009-09-09 | 上海应用技术学院 | Polyacrylate emulsion with high water resistance and preparation method thereof |
| CN108484811A (en) * | 2018-02-28 | 2018-09-04 | 佛山市顺德区巴德富实业有限公司 | A kind of solvent resistant acrylic emulsion and preparation method thereof |
| CN112300318A (en) * | 2020-11-10 | 2021-02-02 | 三棵树(上海)新材料研究有限公司 | Environment-friendly room-temperature self-crosslinking acrylate emulsion, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 魏丽敏等: "有机硅改性醋苯丙防水乳液的制备及性能研究", 《新型建筑材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678374A (en) * | 2023-01-06 | 2023-02-03 | 山东世纪联合新材料科技有限公司 | Water-based heat insulation coating and preparation method thereof |
| CN116876221A (en) * | 2023-07-04 | 2023-10-13 | 广东创新精细化工实业有限公司 | Fluorine-free waterproof agent, preparation method thereof and application thereof in fabric |
| CN116876221B (en) * | 2023-07-04 | 2024-03-08 | 广东创新精细化工实业有限公司 | Fluorine-free waterproof agent, preparation method thereof and application thereof in fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114044847B (en) | 2023-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109868026B (en) | Organic silicon modified acrylate resin, preparation method thereof and hydrophobic weather-resistant slow-release modified acrylic resin coating | |
| CN114044847B (en) | High-water-resistance and dirt-resistance acrylate emulsion and preparation method thereof | |
| EP1989235B1 (en) | Aqueous silica-based nanocomposite polymer dispersion | |
| CN113621103B (en) | Amine-free elastic acrylate emulsion, waterproof coating and preparation method | |
| CN101098902A (en) | Organic copolymers containing nanoparticles | |
| CN107118650B (en) | Silica sol/polyacrylate emulsion containing hydroxyl-amino resin baking varnish and preparation method thereof | |
| CN108727881B (en) | Preparation method of high-adhesion high-flexibility water-based inorganic zinc-rich coating | |
| CN109054570B (en) | Environment-friendly high-strength elastic coating and preparation method thereof | |
| US20110312240A1 (en) | Aqueous binder compositions | |
| CN110183957B (en) | Environment-friendly high-wear-resistance water-based gloss oil and preparation method thereof | |
| CN1730547A (en) | Monocomponent self-cross-linking epoxy acrylic acid composite emulsion , its preparation method and uses | |
| CN102858806A (en) | Method for producing hybrid particles | |
| CN113292682B (en) | Normal-temperature self-crosslinking type acrylate emulsion with core-shell structure, and preparation and application thereof | |
| CN108219652A (en) | A kind of aqueous double-component finishing coat and preparation method thereof | |
| JPS648033B2 (en) | ||
| CN115710335A (en) | High-performance epoxy modified primer emulsion capable of being directly coated and preparation method thereof | |
| CN110294825B (en) | Core-shell type tertiary carbon redispersible latex powder and preparation method thereof | |
| CN102753618A (en) | Hybrid particle made of polymers and nanoparticles | |
| CN103232566B (en) | Preparation method of high-solid-content low-viscosity acrylate emulsion for sealing gum | |
| CN110437776A (en) | A kind of double-component aqueous redwood splicing adhesive and its application | |
| CN108794682B (en) | Normal-temperature ketone hydrazine self-crosslinking acrylic resin emulsion and preparation method and application thereof | |
| CN117700651A (en) | Fluorosilicone modified acrylic resin, preparation method thereof, powder coating containing fluorosilicone modified acrylic resin and application of fluorosilicone modified acrylic resin | |
| CN110790875B (en) | Organic silicon modified acrylic emulsion adhesive and preparation method thereof | |
| CN110003482B (en) | Polyacrylate emulsion for plastic base material and preparation method thereof | |
| CN115124649B (en) | Real stone paint emulsion and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |